CN105593203A

CN105593203A - Method for producing methacrylated benzophenones

Info

Publication number: CN105593203A
Application number: CN201480054472.3A
Authority: CN
Inventors: W·克勒塞; J·克内贝尔; D·萨尔
Original assignee: Evonik Roehm GmbH
Current assignee: Roma Chemical Co ltd; Evonik Oil Additives GmbH; Evonik Operations GmbH
Priority date: 2013-10-04
Filing date: 2014-09-29
Publication date: 2016-05-18
Anticipated expiration: 2034-09-29
Also published as: KR20160067929A; JP2016539913A; ES2769580T3; EP3052467B1; TW201527273A; US20160297738A1; TWI654176B; DE102013220127A1; WO2015049200A1; JP6530384B2; CN105593203B; US9656941B2; EP3052467A1; KR102254784B1

Abstract

The invention relates to a method for producing methacrylic acid esters from hydroxy-functional benzophenones and use thereof. According to the claimed method, methacrylated benzophenones (benzophenon(meth)acrylates) can be produced simply, with high purity and in high yield.

Description

Prepare the method for metering system acidifying benzophenone

Technical field

The present invention relates to the method for the methacrylate of preparing hydroxyl-functional benzophenone and their purposes. By thisThe method of invention can be with high-purity, prepare metering system acidifying benzophenone in simple mode with high yield.

Background technology

Methacrylic anhydride method (JP2003261506, Mi for the preparation of above-mentioned ester have been described in the prior artTsubishiRayon). Use triethylamine as catalyst. Because amine and the methacrylic acid producing in course of reaction formSalt is equimolar amounts so must make itself and benzophenone. Correspondingly, obtain the salt of equimolar amounts, it must be abandoned as refusePut. Therefore the method is less economical. Other method of the prior art is methacrylic chloride and hydroxyl-functional benzophenoneReaction, and the reacting of this raw material and GMA. While adopting methacrylic chloride, must be noted that corruptionErosion and causticity character. In addition,, in the time contacting with water, discharge HCl.

DE1720603 has described the method for preparing the aqueous dispersion of polymer that can be easily crosslinked. Wherein make acrylateWith methacrylate and photoactive ethylenically unsaturated monomers, especially comprise benzophenone derivates, carry out copolymerization, optionalUse photolytic activity nonionic emulsifier simultaneously.

EP0346788 has described preparation and has had the radiosensitive of at least one methacrylate or acrylate end groupsCarbamyl benzophenone and the method for carbamyl acetophenone. Wherein use base catalyst to make (methyl) acrylic acid isocyanideAcidic group Arrcostab and hydroxy acetophenone or hydroxy benzophenone reactive ketone. Must under the condition of getting rid of moisture, operate at this. In addition,Only to use the non-nucleophilic solvent of drying.

WO2010/072479 has described under the sulfuric acid of catalytic amount exists and has prepared above-mentioned ester. In the time that reaction finishes, necessaryNeutralize this catalyst and must be by removing by filter sodium sulphate with sodium hydroxide solution.

In the case of the esterification of salt catalysis, make to want the alcohol of esterification and carboxylic acid anhydrides a small amount of this acid anhydrides based on sour saltThere is lower reaction. According to DE3601098 or Autorenkollektiv, Organikum, the 20th edition, 1999, the 444-445Page can carry out esterification by sugar thus and become acetic acid esters under acetic anhydride exists with sodium acetate. But, need a large amount of catalyst and/Or acylating agent. Make 20% anhydride reaction of the leucoalizarin similar to 4-dihydroxy benaophenonel and its mole, maybe must useThe acetic anhydride of 3.3 times of molar excess is acetylation (people such as H.P.Faro, Arch.Pharm.313,800 under sodium acetate exists(1980)). In sugared esterification, use a large amount of excessive acylating agents (1.76mol/mol).

Summary of the invention

Therefore, the object of this invention is to provide the preparation method of further simplification, wherein can be without additional step (for exampleNeutralization) separate and remove catalyst and wherein must only thereupon have low salt load.

The method of preparing benzophenone (methyl) acrylate by one has realized this object, it is characterized in that making hydroxylThe reaction under the salt of catalytic amount exists of benzophenone and (methyl) acrylic anhydride, wherein (methyl) acrylic anhydride and hydroxy benzophenoneThe amount of ketone is than being 1.0:1.0 to 1.6:1.0.

Statement " (methyl) acrylate " is finger methacrylate at this, for example methyl methacrylate, methyl-propOlefin(e) acid ethyl esters etc., refer to again acrylate, such as methyl acrylate, ethyl acrylate etc., and both mixtures.

Find surprisingly, can realize high conversion degree by method of the present invention. Method of the present invention also only relates toAnd low salt load. Can easily isolate this salt.

In a kind of particular, (methyl) acrylic acid generating as accessory substance is at benzophenone monomer subsequentlyIn polymerization, be used simultaneously as comonomer. In another embodiment, (methyl) acrylic acid is recycled for preparationNew (methyl) acrylic anhydride.

In a kind of preferred embodiment, (methyl) acrylic anhydride is positioned at 1.0 with the amount ratio of dihydroxy benaophenonel:In 1.0 to 1.6:1.0 scope. In another embodiment, this ratio is positioned at the scope of 1.1:1.0 to 1.4:1.0, more excellentBit selecting is in the scope of 1.1:1.0 to 1.2:1.0. (methyl) acrylic anhydride is more special than very with the amount of dihydroxy benaophenonelBe preferably 1.1:1.0.

Use in one embodiment multiple dihydroxy benaophenonel. Particularly preferably be in this case selected from 4-,The dihydroxy benaophenonel of 3-or 2-dihydroxy benaophenonel and/or their isomer mixture or other mixture, and two officialCan dihydroxy benaophenonel, as 2,3-, 2,4-or 4,4'-dihydroxy benaophenonel and/or their isomer mixture or otherMixture.

In another embodiment, use the mixture of methacrylic anhydride and acrylic anhydride.

In a kind of particular, make 4-dihydroxy benaophenonel and methacrylic acid anhydride reactant to produce 4-(methylAcryloxy) benzophenone.

In a kind of preferred embodiment, use sodium acetate as catalyst. Corresponding lithium acetate or potassium acetate and/orLi-, Na-or K-(methyl) acrylates is also suitable. Particularly preferably use Sodium methacrylate. In another embodimentIn, by corresponding methoxide and/or by their methanol solution at the acetic acid by adding and/or by (methyl) acrylic acid existingThe course of reaction situ of acid anhydride generates described salt. Alternative also can be added corresponding salt in this reaction to after preparing separately.

In a kind of preferred embodiment, this catalyst is in 0.2 to 5.0 of the amount of (methyl) used acrylic anhydride% by mole amount use. In another embodiment, this catalyst with the amount of (methyl) used acrylic anhydride 0.3 to4.0 % by mole, preferably 0.45 to 2.5 % by mole, more preferably 0.5 to 2.3 % by mole or until the amount use of 0.7 % by mole. ?In a kind of particularly preferred embodiment, this catalyst is in 0.5 % by mole of the amount of (methyl) used acrylic anhydrideAmount is used.

Adopt method of the present invention, can obtain benzophenone (methyl) acrylate with solid form. Preferred in oneIn embodiment, make described one or more dihydroxy benaophenonels and described one or more (methyl) acrylic anhydrides 50 to120 DEG C, more preferably 70 to 110 DEG C, more more preferably 85 to 95 DEG C or 90 to 100 DEG C, very particularly preferably anti-at the temperature of 90 DEG CShould.

Preferably, the reaction time is 1 to 13 hour especially at 90 DEG C, more preferably 1.5 to 11 hours, more more preferably 4 to 8 littleTime.

Optionally after the hydrolysis of excessive (methyl) acrylic anhydride, for example, by adding methyl alcohol or by being stirred in water, carrying outThe follow-up post processing of rough monomer. Like this, water-solubility impurity dissolves and can isolate without problems. By benzophenone (methyl) thirdOlefin(e) acid ester precipitates and passes through and filters with isolated in solid form in water.

Benzophenone (methyl) acrylate of preparing with high-purity can with methyl methacrylate, methacrylic acid justButyl ester, isobutyl methacrylate or styrene store with dissolved form together, the single step reaction of going forward side by side.

Adopt method of the present invention, can obtain equally the benzophenone (first in (methyl) acrylic acid alkyl ester solutionBase) acrylate. Other suitable solution is styrene solution. In a kind of preferred embodiment, first by described one orMultiple dihydroxy benaophenonel and described one or more (methyl) acrylic anhydrides, catalyst and optional stabilizing agent mix. ThenRegulate desired reaction temperature. In a kind of preferred embodiment, make described one or more dihydroxy benaophenonels and described oneOr multiple (methyl) acrylic anhydride is at 50 to 120 DEG C, more preferably 70 to 110 DEG C, more more preferably 85 to 95 DEG C or 90 to 100 DEG C,Very particularly preferably at the temperature of 90 DEG C, react. In order to prepare described solution in (methyl) alkyl acrylate, in reactionAfter completing, add (methyl) alkyl acrylate and/or its optional mixture, to obtain the benzophenone (first of desired concnBase) acrylate. After this use suitable pressure filter to isolate salt and impurity.

Preferably, the reaction time is 2 to 8 hours especially at 90 DEG C, more preferably 3 to 7 hours, more more preferably 4 to 8 hours,More especially 4.5 to 5.5 hours.

Should be preferably selected from (methyl) methyl acrylate, n-BMA or methyl-prop by (methyl) alkyl acrylateOlefin(e) acid isobutyl ester. Suitable in addition also have (methyl) acrylic acid hydroxy alkyl ester, more especially (methyl) hydroxy-ethyl acrylate and/or(methyl) hydroxypropyl acrylate. Particularly preferably be methyl methacrylate (MMA).

Therefore the theme of this patent also has benzophenone (methyl) acrylate in (methyl) alkyl acrylate or benzene secondThe preparation of the solution in alkene. In a kind of preferred embodiment, the 4-(metering system of the MMA solution form of preparation 30% concentrationAcyloxy) benzophenone.

Benzophenone (methyl) acrylate can be used for by the follow-up photocrosslinking of daylight or ultraviolet polymer withAnd as polymeric photoinitiators.

In addition, benzophenone (methyl) acrylate can be used as monomer and/or the comonomer for polymerisation.

The following example is intended to explain more in detail the present invention, but is not limited to feature disclosed herein.

Detailed description of the invention

Embodiment

Abbreviation:

MAAH (methyl) acrylic anhydride

MeOH methyl alcohol

MMA methyl methacrylate

MAA methacrylic acid

NM30 solution sodium methoxide, 30% concentration in methyl alcohol, Evonik company

The area percentage that GC area % draws by gas chromatography

GC; The percentage by weight that % by weight draws by gas chromatography

HQME Hydroquinone monomethylether

AN is in the acid number of mgKOH/g

TopanolA2,4-dimethyl-6-tert-butyl phenol (polymerization inhibitor)

Gas chromatographic analysis: instrument: with the Agilent7820A of FID

Capillary column DB5,30 meters long, 0.25 millimeter of diameter, layer thickness 0.25 μ m

250 DEG C of injector temperature, 300 DEG C of detector temperatures

Temperature program(me): 80 DEG C of 2min, be then heated to 300 DEG C with 16 DEG C/min, keep this temperature 6min.

Embodiment 1: generated in-situ methacrylic acid sodium catalyst

Device: 2 liter of four neck round-bottomed flask, passes with mechanical stirring device, reflux condenser, air intake, Pt100 temperatureSensor, oil bath.

Batch of material: 1.5 moles of (297.9 grams) 4-dihydroxy benaophenonels, 1.65 moles of (270.3 grams) MAAH, 0.0087 mole(1.6 grams) NM30 solution, 399 milligram 2,4-dimethyl-6-tert-butyl phenol (TopanolA);

The preparation of the 30% concentration solution of 4-(methacryloxy) benzophenone in MMA: add 772 grams altogetherMMA

The theoretical yield of 4-(methacryloxy) benzophenone: 399 grams

Implementation procedure: be weighed into 4-dihydroxy benaophenonel and add wherein 126 grams of MMA that need subsequently; Formation can be easyThe composition stirring. Then add MAAH, stabilizer T opanolA and catalyst n M30, introduce air and this batch of material is heatedTo 90 DEG C. (sample thief (about 1.5 milliliters), by about 5 milliliters of acetone diluted, mistake to monitor reaction process by gas chromatographyFilter). At 90 DEG C, altogether after 5 hours, this batch of material is cooled to 60 DEG C, adds 30 grams of methyl alcohol to transform residue MAAH, and shouldBatch of material stirs 1 hour at 60 DEG C. Then will remain MMA (646 grams) and add in this batch of material, to prepare the molten of 30% concentrationLiquid. Under agitation cooling, and through with filter course SeitzT1000 () pressure filter filter. Output:1320.4 gram

Analyze:

Water content according to KarlFischer: 0.03%

TopanolA:538ppm

GC area %:52.543%MMA

9.491％MAA

0.829%4-dihydroxy benaophenonel

0.701%4-acetoxyl group benzophenone

34.921%4-(methacryloxy) benzophenone

GC; % by weight: MMA57.9%

MAA10.9％

4-(methacryloxy) benzophenone 28.5%

Hazen look number: 315

AN:69＝10.58％MAA

Embodiment 2: the 4-(methacryloxypropyl of preparing solid form with the methacrylic acid sodium catalyst that original position producesBase) benzophenone

Device: see embodiment 1

Batch of material: 4.0 moles of (794.7 grams) 4-dihydroxy benaophenonels, 4.4 moles of (723.7 grams) MAAH, 0.0228 mole(4.2 grams) NM30 solution, 1055 milligrams of TopanolA;

Theoretical yield: 4-(methacryloxy) benzophenone: 1055.2 grams

Implementation procedure: be weighed into batch of material completely, be then heated to 90 DEG C. After 6 little the reaction times, 4-dihydroxy benaophenonelRatio is still 2.2% (GC analysis); Follow-up add 2 milliliters of NM30 solution and continue heating. At 90 DEG C altogether after 11 hours, willThis batch of material is cooled to 60 DEG C and add 80 grams of methyl alcohol with by unreacted MAAH esterification. Subsequently this batch of material is stirred to 1 at 60 DEG CHour. Then by this batch of material under agitation (metal dasher, stirring motor) pour in 3 premium on currency with thin pattern. StirMix 0.5 hour, then pass through suction filtration sediment separate out via sintered glass filter, follow-up again with 2.0 premium on currency washings oneInferior (in glass beaker, use with the stirring motor of metal dasher and stir 30 minutes), then on suction filter, suction is dryDry. Subsequently by this solid at air drying until constant-quality. Output: 1042.3 grams

Analyze:

Water content (KarlFischer): < 0.1%

TopanolA:808ppm

GC:0.066％MAA

1.239%4-dihydroxy benaophenonel

1.785%4-acetoxyl group benzophenone

95.574%4-(methacryloxy) benzophenone

Hazen look number, 20% concentration in acetone: 154

Embodiment 3: the 4-(methacryloxypropyl of preparing solid form with the methacrylic acid sodium catalyst of preparation separatelyBase) benzophenone

Device: see embodiment 1

Batch of material: 0.5 mole of (99.4 grams) 4-dihydroxy benaophenonel, 0.55 mole of (88.3 grams) MAAH, 0.0125 mole(1.35 grams) Sodium methacrylate, 133 milligrams of HQME, 133 milligrams of TopanolA;

The theoretical yield of 4-(methacryloxy) benzophenone: 133.15 grams

Implementation procedure: be weighed into batch of material completely, be then heated to 90 DEG C under the condition of introducing air. Pass through gas chromatography(GC) monitoring transforms. Composition after 1.5 hours: 18.42%MAA, 2.5%MAAH, 0.83% dihydroxy benaophenonel,75.84%4-(methacryloxy) benzophenone. Be cooled to 60 DEG C, add methyl alcohol (10 grams) and by this batch of material at 60 DEG CStir 1 hour.

Then by this batch of material under agitation (metal dasher, stirring motor) pour 500 milliliters into thin patternIn water. Stir 0.5 hour, then through sintered glass filter by suction filtration sediment separate out, follow-uply use again each 500 millilitersTwice of water washing (use in glass beaker with the stirring motor of metal dasher at every turn and stir 15 minutes), is then inhalingSuction dried on filter. Subsequently by this solid at air drying until constant-quality. Output: 131.1 grams

Analyze:

Water content according to KarlFischer: 0.21%

HQME:13ppm

TopanolA:1305ppm

GC:0.012％MMA

0.331％MAA

1.573%4-dihydroxy benaophenonel

94.594%4-(methacryloxy) benzophenone

Look number, 20% concentration in acetone: 82

Embodiment 4: prepare 4-(methacryloxy) benzophenone with methacrylic acid sodium catalyst; Transform tester

Device: see embodiment 1

Batch of material: 0.5 mole of (99.4 grams) 4-dihydroxy benaophenonel, 0.55 mole of (88.3 grams) MAAH, 0.003 mole(0.32 gram) Sodium methacrylate, 133 milligrams of HQME, 133 milligrams of TopanolA;

The theoretical yield of 4-(methacryloxy) benzophenone: 133.15 grams

Implementation procedure: be weighed into batch of material completely, be then heated to 90 DEG C. By GC, monitoring transforms.

Composition in % by weight:

Reaction time	MAA	MAAH	Dihydroxy benaophenonel	4-(methacryloxy) benzophenone
					1h	16.69	6.47	4.66	69.72
2h	18.03	4.39	2.83	72.07 5 -->
					3h	18.95	3.46	1.21	73.96
4h	17.69	2.96	1.25	74.88

Be cooled to 60 DEG C, add methyl alcohol (9.6 grams) will remain MAAH esterification, and this batch of material is stirred at 60 DEG C 1 littleTime. Then by this batch of material under agitation (metal dasher, stirring motor) pour in 500 ml waters with thin pattern.Stir 0.5 hour, then through sintered glass filter by suction filtration sediment separate out, follow-uply use again each 500 milliliters of washingsWash twice (in glass beaker, use with the stirring motor of metal dasher and stir about 15 minutes at every turn), then inhalingSuction dried on filter.

Subsequently by this solid at air drying until constant-quality. Output: 136.7 grams

Analyze:

H₂O:0.25％

HQME:15ppm

TopanolA:1530ppm

GC:1.064％MAA

2.571%4-dihydroxy benaophenonel

92.754%4-(methacryloxy) benzophenone

Look number, 20% concentration in acetone: 144

Embodiment 5: sodium acetate catalyst

Device: 2 liter of four neck round-bottomed flask, with mechanical agitator, reflux condenser, air intake pipe and Pt100 temperatureSensor, oil bath

Batch of material:

0.5 mole of 4-dihydroxy benaophenonel, purity 99.9%=99.2g

0.55 mole of methacrylic anhydride, purity 97.7%=86.9g

0.0125 mole of acetic acid sodium, anhydrous=1.025g

TopanolA＝93.2mg

For the excessive methacrylic acid of esterification: 9.6 grams of methyl alcohol

The theoretical yield of 4-(methacryloxy) benzophenone: 133.2 grams

Implementation procedure: be weighed into 4-dihydroxy benaophenonel. Then add methacrylic anhydride, TopanolA and sodium acetate, withAfter under air-supplied condition, this batch of material is heated to 90 DEG C. Stirred 6 hours, be then cooled to 60 DEG C, and added firstAlcohol is for esterification residue methacrylic anhydride. At 60 DEG C, stir 1 hour in addition. Then this batch of material is under agitation introduced to 500Milliliter H₂In O, stir 0.5 hour, suction filtration washs solid once with 500 ml waters in glass beaker again, then existsSuction dried on suction filter. Product is at air drying.

Output: 130 grams of 4-(methacryloxy) benzophenone

Analyze:

Water content: 0.36%TopanolA:1390ppm

Hazen look number (in acetone 10%): 16

GC area %:0.011%MMA

0.650％MAA

1.834%4-dihydroxy benaophenonel

2.928%4-acetoxyl group benzophenone

91.560%4-(methacryloxy) benzophenone

Claims

1. prepare the method for benzophenone (methyl) acrylate, it is characterized in that making dihydroxy benaophenonel and (methyl) acrylic acidAcid anhydride reaction under the salt of catalytic amount exists, wherein (methyl) acrylic anhydride is 1.0:1.0 with the amount ratio of dihydroxy benaophenonelTo 1.6:1.0.

2. according to the process of claim 1 wherein that described amount is than the scope that is positioned at 1.05:1.0 to 1.5:1.0, preferablyBe positioned at the scope of 1.1:1.0 to 1.4:1.0, be more preferably positioned at the scope of 1.1:1.0 to 1.2:1.0.

3. according to the method for claim 1 or 2, wherein use 4-dihydroxy benaophenonel as dihydroxy benaophenonel.

4. according to the method for aforementioned claim any one, wherein use methacrylic anhydride or acrylic anhydride.

5. according to the method for aforementioned claim any one, wherein use Sodium methacrylate as catalyst.

6. according to the method for aforementioned claim any one, wherein said catalyst uses with the amount of 0.2 to 5.0 % by mole.

7. according to the method for aforementioned claim any one, wherein said reaction is carried out at the temperature of 50 to 120 DEG C.

8. according to the method for aforementioned claim any one, wherein said reaction is carried out 1 to 13 hour.

9. according to the method for aforementioned claim any one, wherein in water, precipitate described benzophenone (methyl) acrylate.

According to the benzophenone obtaining in the method for aforementioned claim any one (methyl) acrylate as monomerAnd/or comonomer is for the purposes of polymerization.

11. according to the benzophenone obtaining in the method for claim 1 to 9 any one (methyl) acrylate for polymerFollow-up photocrosslinking, be preferred for the purposes by daylight or ultraviolet follow-up photocrosslinking.

12. according to the benzophenone obtaining in the method for claim 1 to 9 any one (methyl) acrylate as polymerThe purposes of light trigger.